Acidic esters of oxypropylated triamines



Patented May 25, 1954 UNITED STATES a'rrur :oFrieE IACIDIC 'ESTERS OF OXYPROPYLATED TRIAMIN ES ware No Drawing. Application May 14, 1951, Serial No. 226,311

10 Claims. (01.260-475) The present invention is .a -zcontinuation-in- Part of my copending applications, Serial Nos. 104,801 filed Jul 14, 1949 (now Patent 2,552,528, granted May 15, 19.51), 109,619, .filed August 10, 1949 (now Patent 2,552,531, granted May 15, 1951), and l 7,3 81,filed Ju1 '28,11949 (now Patent 2,552,530, granted Mayl5, 1951).

The present inventionis concerned with certain new chemical products, compounds, or compositions which have usefulapplication in various arts. It includes methods or proceduresformanufacturing said new chemical products, compounds or compositions, as Well as the products, compounds, or compositions themselves.

Complementary to the above aspect of the invention herein disclosed is my companion invention concerned with the use of these particular chemical compounds, or products, as demul sifying agents in processes or proceduresparticw larly adapted for preventing, breaking, or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions. See my 00- pending application, Serial No. 228,310, filed 'May 14, 1951, now Patent No. 2,626,918.

Said last aforementioned co-pending application, 1. e., Serial No. 107,381, now Patent No. 2,552,530, is concerned, among other things, with high molal oxypropylation derivatives of monomerio polyainino compounds with the proviso that (a) the initial polyamino reactant be free from radical havingat least 8 uninterrupted carbon atoms; (1)) the initial'p'olyamino reactant have a molecularweight of not over 1800 and at least a plurality of reactive hydrogen atoms; (0) the initial polyamino reactant must be water-soluble; (d) the oxypropylation end product must be water-insoluble; (e) the oxypropylation end product be Within'the molecular weight range of 2000 to 30,000 on an average statistical basis; (7) the solubility characteristics of the oxypropylation end product in respect to Water must be substantially "the result of the oxyprop'ylation step; (g) the ratio of propylene oxide per initial reactive hydrogen atom must be within the range of '7 to 7; (h) the initial polyamino reactant must represent "not more than20% by weight of the oxypropylati'on end product "on 'a statistical basis; the preceding provisos are based on the assumption 'of complete reaction involving the propylene oxide and initial polyamino reactant; (7') the polyamino'reactantmus't contain at least one 'basic nitrogen atom; and (7c) the nitrogen atoms are "linked by a carbon atom chain.

Furthermore, in said aforementioned co-pending application it was pointed out that such hydroxylated materials obtained -by 'oxypropylation could be reacted with dicarboxy acids such as 2 cliglycollic acid to yield valuable derivatives which aresatis'factory also for demulsification' of petroleum emulsions.

"What is said herein is-concerned with a fractional ester obtained from a polycarboxy acid and a polyhydroxylatedmaterial obtaine'd by the oxypropylation of a 'polyamino reactant.

More specifically, the present invention isconcerned with a fractional "ester obtained from a polycarb'oxy acid and a compoundderived in turn by the oxypropylation of 'dipropylenetriamine or an equivalent triamine as hereinafter specified, having five terminal hydroxy radicals or the amine "treated with-oneto five, six-or seven moles of ethylene oxide. The initial triamino compound must be characterized by (a) having 3 amino nitrogen atoms and preferably all being basic; (1)) free from'any radical having 8 or more carbon atoms in an uninterrupted group; (0) must be water-soluble; and (it) have a plurality of reactive hydrogen atoms, preferably at least 3'or 4.

Needless to say, the most readily available reactant, to wit, -'dipropylenetriamine, has 5 reactive hydrogen atoms and this still would be true after reaction with ethylene oxide, for instance, 5 moles -of ethylene oxide. However, reaction with glycide would provide as many as 10 reac tive hydrogen atoms provided that the molal raradical such-as 'methyl,ethyl, propyl, -butyl,'hexyl, heptyl, or the like, or an aryl radical such as a phenyl radical, then and in that event the numwould not be materially airec'ted. However, the introduction of a phenyl radical would, of course, markedly afiect the basicity of the nitrogen atom. For obvious reasons my choice is as follows:

(a) The use of dipropylenetriamine rather than any substituted dipropylenetriamine as described;

(b) The use of dipropylenetriamine after treatment with 1 to 5 moles of ethylene oxide although a modestly increased amount of -ethyl ene oxide can be used in light or what is said hereinafter; or

(c) The use of a derivative obtained from dipropylenetriamine after reaction with glycide, or a mixture of ethylene oxide and glycide.

Since reaction of dipropylenetriamine with propylene oxide is invariably involved and since this oxyalkylation step is substantially the same as the use of ethylene oxide of glycide, for the purpose of brevity further reference simply will be made to dipropylenetriamine as illustrating the procedure, regardless of what particular reactant is selected. It is not necessary to point out, of course, that the substituted dipropylenetriamine, i. e., those where an alkyl, alicyclic, aryl-alkyl, or aryl group has been introduced can similarly be subjected to reaction with ethylene oxide, glycide, or a combination of the two.

I also want to point out it is immaterial whether the initial oxypropylation step involves hydrogen attached to oxygen or hydrogen attached to nitrogen. The essential requirement is that it be a labile or reactive hydrogen atom. Any substituent radical present must, of course, have less than 8 uninterrupted carbon atoms in a single group.

More specifically, then, the present invention is concerned with hydrophile synthetic products; said hydrophile synthetic products being the acidic fractional esters derived by reaction between (A) a polycarboxy acid and (B) high molal oxypropylation derivatives of monomeric triamino compounds, with the proviso that (a) the initial triamino reactant be free from any radical having at least 8 uninterrupted carbon atoms; (b) the initial triamino reactant have a molecular weight of not over 800 and at least a plurality of reactive hydrogen atoms; the initial triamino reactant must be water-soluble; (d) the oxypropylation end product must be water-insoluble, and kerosene-soluble; (e) the oxypropylation end product be within the molecular weight range of 2,500 to 30,000 on an average statistical basis; (1) the solubility characteristics of the oxypropylation end product in respect to water and kerosene must be substantially the result of the oxypropylation step; (9) the ratio of propylene oxide per initial reactive hydrogen atom just be within the range of "I to 70; (71.) the initial triamino reactant must represent not more than by weight of the oxypropylation end product on a statistical basis; (1') the preceding provisos are based on the assumption of complete reaction involving the propylene oxide and initial triamino reactant; (j) the nitrogen atoms are linked by a propylene chain, and with the further proviso that the ratio of (A) to (B) be one mole of (A) for each hydroxyl radical present in (B).

What has been said previously in regard to the materials herein described and particularly for use as demulsifiers with reference to fractional esters may be and probably is an oversimplification for reasons which are obvious on further examination. It is pointed out subsequently that prior to esterification the alkaline catalyst can be removed by addition of hydrochloric acid. Actually the amount of hydrochloric acid added is usually suflicient and one can deliberately employ enough acid, not only to neutralize the alkaline catalyst but also to neutralize the amino nitrogen atom or convert it into a salt. Stated another way, a trivalent nitrogen atom is converted into a pentavalent nitrogen atom, i. e., a change involving an electrovalency indicated as follows:.

wherein HX represents any strong acid or fairly strong acid such as hydrochloric acid, nitric acid, sulfuric acid, a sulphonic acid, etc., in which H represents the acidic hydrogen atom and X represents the anion. Without attempting to complicate the subsequent description further it is obvious then that one might have esters or one might convert the esters into ester salts as described. Likewise another possibility is that under certain conditions one could obtain amides. The explanation of this latter fact resides in this observation. In the case of an amide, such as acetamide, there is always a question as to whether or not oxypropylation involves both amido hydrogen atoms so as to obtain a hundred per cent yield of the dihydroxylated compound. There is some evidence to at least some degree that a monohydroxylated compound is obtained under some circumstances with one amido hydrogen atom remaining without change.

Another explanation which has sometimes appeared in the oxypropylation of nitrogen-containing compounds particularly such as acetamide, is that the molecule appears to decompose under conditions of analysis and unsaturation seems to appear simultaneously. One suggestion has been that one hydroxyl is lost by dehydration and that this ultimately causes a break in the molecule in such a way that two new hydroxyls are formed. This is shown after a fashion in a highly idealized manner in the following way:

In the above formulas the large X is obviously not intended to signify anything except the central part of a large molecule, whereas, as far as a speculative explanation is concerned, one need only consider the terminal radicals, as shown. Such suggestion is of interest only because it may be a possible explanation of how an increase in hydroxyl value does take place which could be interpreted as a decrease in molecular weight. This matter is considered subsequently in the final paragraphs of Part 2. This same situation seems to apply in the oxypropylation of at least some polyalkylene amines and thus is of significance in the instant situation.

In the case of higher polyamines there is evidence that all the available hydrogen atoms are not necessarily attacked, at least under comparatively modestoxypropylation conditions, particularly when oxypropylation proceeds at low temperature as herein described, for instance, about the boiling point of water. For instance, in the case of diethylene triamine there is some evidence that one terminal hydrogen atom only in each of the two end groups is first attacked by propylene oxide and then the hydrogen atom attached to the central nitrogen atom is attacked. It is quite possible that three long propyleneoxide chains are built up before the two remaining :hydrogens are attacked -and perhaps not attacked :at all. .This, ofccoursegdependson the conditions .of voxypropylation. :However, analytical procedure :is not :entirely .satisfactory in some instances difierentiating between a reactive hydrogen atom attached .to nitrogen and a reactive hydrogenatonrattached to-oxygen.

In the case of .triethylenetetramine :the same situation seems to .follow. One.:hydrogen atom on the two terminal groups .isifirst attacked .and then the two hydrogenatoms .1011 theztwojintermediate nitrogen atoms. .I'hus .four ichains:tend to build up and perhaps :finally, .if at all, the remaining :two hydrogen atoms attached to the then finally, if at all depending on conditions of .oxypropylation, the two remaining terminalhydrogen atoms are attacked.

If this is the case it is purely a matter of speculation at the momentbecause apparently there is no data which determines the matter completely under all conditions of manufacture, and one has a situation somewhat comparable to the acylation of monoethanolamine or diethanolamine, i. e., acylation can take place involving either the hydrogen atom attached to oxygen or the hydrogen atom attached to nitrogen.

As far as the herein described compounds are concerned it would be absolutely immaterial except that one would have in part a compound which might be the fractional ester and might also represent an amide in which only one carboxyl radical of a polycarboxylated reactant was involved. By and large, it is believed that the materials obtained are obviously fractional esters, for reasons which are apparent in light of what has been said and in light of .what appears hereinafter.

What has been said in regardto the reactions involving polyethyleneamines obviously is true in regard to polypropyleneamines.

However, in order'to presenttheinventionin its broadest aspect it 'had best be reestated as follows: It is concerned with certainhydrophile synthetic products; said .hydrophile synthetic products being a cogenericmixture selected from the class consisting of acidic fractional esters, acidic ester salts, .and acidic amidoderivatives obtained by reaction between (A) a polycarboxy acid, and (B)) high molaloxypropylationderivatives of monomeric triamino compounds, with the proviso that (a) the initial triamino reactant be free from-any radical having at least 8 uninterrupted carbon atoms; (b) the initial triamino reactant have a molecular weight of not over 800 and at least a plurality of reactive hydrogen atoms; the initial triamino reactant must be water-soluble; (d) the oxypropylation end product must be water-insoluble, and kerosene-soluble; (e) the oxypropylation end product be within the molecular weight range of 2500 to 30,000 on an average statistical basis; (1) the solubility characteristics of the oxypropylation end product in respect .to water and kerosene must be substantially the result of the .oxypropylation step; (9) the ratio of propylene oxide per initial reactive hydrogenatom-must. be within the range of .7 to .70; (h) the initial triamino reactant must represent not more .thani20% by weight of the-oxypropylation end product on a statistical .:basis; .16) the :preceding gprovisos .are based on .theassumptionrofcomplete reaction involving the propylene .-'oxide initial diamino reactant; (:i) the nitrogen atomsare linked by a propylene chain, and with .thefinalproviso that the ratio of (A) to (B) Ibe one.mole of .(A) .for each hydroxyl radical .presentin .QB)

Although the :herein :described .products have a number ofindustrialapplications,they are .of particular :value for .resolving petroleum emulsions of the .watersineoilztypecthat arexcommonly referred to as cut oil, roily.oil; fiemulsified oil, etc, and which :comprise 'fine:;droplets of naturally-occurring :waters -:or ibrines .dispersed in a more or less .permanentstate throughout the oil which. constitutes .the'continuous phaselofthe emulsion. This specific application .isdescribed and claimed in myco-Lpending application,:.Serial N 0. 226,310, filed May 1 .4,1'1951, :now :Patent .No. 2,626,918.

The new products are usefulas :wetting, detergent and leveling agents :in the .laundry, textile and dyeing industries; as wet detergents in theacidwashing and brick; as .wetting-agentsand spreadersrinthe application of asphalt in road buildingand the like; as afiotation reagent=inthe flotation separation of various aqueoussuspensions containing negatively charged particles, suchas sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for vexample, for cosmetics, spray oils, water-repellent textile finishes, as lubricants, etc.

For convenience, what said-hereafter will be divided into four parts:

Part 1 is concerned'with the preparationof the oxypropylation derivatives of -dipropylenetriamine or equivalent initial reactants Part 2 is concerned with the :preparation of the esters from the oxypropylatedderivatives;

Part 3 is concerned withthenature of the oxypropylation derivatives insofar that such cogc neric mixture is invariably-obtainedgand Part 4 is-concerned with the use :of certain valuable derivatives which can be obtained readily from the herein described "fractional :esters.

. PART 11 For a number of well known reasons .equipment, whether laboratory size,-.=semi pilot plant size, pilot plant SIZGVOI' :large scale :size,;is notas a rule designed foraparticularalkylene oxide. Invariablyand inevitably, however, or particularly in the case of laboratory equipment :and pilot plant size the design issuchasito :use any of the customarily available alkylene oxides, i. e., ethylene oxide, propylene .oxide, .butylene oxide, glycide, epichlorohydrin, sstyrene oxide, etc. In the subsequen ldescriptionpfthe equipment it becomesobvious (that it adapted for oxyethylation as well :as oxypropylation.

Oxypropylations are :conducted under a wide variety of conditions, not onlyrinsregard .topresence or absence of catalyst, :and the .kind of catalyst, but also in regard :to the time of reaction, etc. For instance, .oxyalkylations can be conducted at temperatures *up .to approximately 200 C. with pressures in about the same range up to about 200 pounds per square inch. They can be conducted alsoat temperatures approximating the boiling point of water or slightly above, as for example -to C. vUndersuch circumstances the pressure 'will be less than 30 pounds per square .inch :unless somespecial ,pro-

cedure is employed as is sometimes the case, to wit, keeping an atmosphere of inert gas such as nitrogen in the vessel during the reaction. Such low-temperature-low reaction rate oxypropylations have been described very completely in U. S. Patent No. 2,448,664 to H. R. Fife, et al., dated September '7, 1948. Low temperature, low pressure oxypropylations are particularly desirable where the compound being subjected to oxypropylation contains one, two or three points of reaction only, such as monohydric alcohols, glycols and triols.

The initial reactants in the instant application contain at least 2 reactive hydrogens and for this reason there is possibly less advantage in using low temperature oxypropylation rather than high temperature oxypropylation. However, the reactions do not go too slowly and this particular procedure was used in the subsequent examples.

Since low pressure-low temperature-low-reaction-speed oxypropylations require considerable time, for instance, 1 to '7 days of 24 hours each to complete the reaction they are conducted as a rule whether on a laboratory scale, pilot plant scale, or large scale, so as to operate automatically. The prior figure of seven days applies especially to large-scale operations. I have used conventional equipment with two added automatic features; (a) a solenoid control valve which shuts off the propylene oxide in event that the temperature gets outside a predetermined and set range, for instance, 95 to 120 C., and (b) another solenoid valve which shuts off the propylene oxide (or for that matter ethylene oxide if it is being used) if the pressure gets beyond a predetermined range, such as 25 to 35 pounds. Otherwise, the equipment is substantially the same as is commonly employed for this purpose where the pressure of reaction is higher, speed of reaction is higher, and time of reaction is much shorter. In such instances such automatic controls are not necessarily used.

Thus, in preparing the various examples I have found it particularly advantageous to use laboratory equipment or pilot plant equipment which is designed to permit continuous oxyalkylation whether it be oxypropylation or oxyethylation. With certain obvious changes the equipment can be used also to permit oxyalkylation involving the use of glycide where no pressure is involved except the vapor pressure of a solvent, if any, which may have been used as a diluent.

As previously pointed out the method of using propylene oxide is the same as ethylene oxide. This point is emphasized only for the reason that the apparatus is so designed and constructed as to use either oxide.

The oxypropylation procedure employed in the preparation of the oxyalkylated derivatives has been uniformly the same, particularly in light of the fact that a continuous automatically-controlled procedure was employed. In this procedure the autoclave was a conventional autoclave made of stainless steel and having a capacity of approximately gallons and a working pressure of one thousand pounds gauge pressure. This pressure obviously is far beyond any requirement as far as propylene oxide goes unless there is a reaction of explosive violence involved due to accident. The autoclave was equipped with the conventional devices and openings, such as the variable-speed stirrer operating at speeds from 50 R. P. M. to 500 R. P. M.; themometer well and thermocouple for mechanical thermometer;

emptying outlet; pressure gauge, manual ventline; charge hole for initial reactants; at least one connection for introducing the alkylene oxide, such as propylene oxide or ethylene oxide, to the bottom of the autoclave; along with suitable devices for both cooling and heating the autoclave, such as a cooling jacket, and, preferably, coils in addition thereto, with the jacket so arranged that it is suitable for heating the steam or cooling with water and further equipped with electrical heating devices. Such autoclaves are, of course, in essence small-scale replicas of the usual conventional autoclave used in oxyalkylation procedures. In some instances in exploratory preparations an autoclave having a smaller capacity, for instance, approximately 3 liters in one case and about 1% gallons in another case, was used.

Continuous operation, or substantially continuous operation, was achieved by the use of a separate containerv to hold the alkylene oxide being employed, particularly propylene oxide. In conjunction with the smaller autoclaves, the container consists essentially of a laboratory bomb having a capacity of about one-half gallon, or somewhat in excess thereof. In some instances a larger bomb was used, to wit, one having a capacity of about one gallon. This bomb was equipped, also, with an inlet for charging, and an eductor tube going to the bottom of the container so as to permit discharging or alkylene oxide in the liquid phase to the autoclave. A bomb having a capacity of about 60 pounds was used in connection with the 15-gallon autoclave. Other conventional equipment consists, of course, of the rupture disc, pressure gauge, sight feed glass, thermometer, connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use. The connections between the bomb and the autoclave were flexible stainless steel hose or tubing so that continuous weighings could be made without breaking or making any connections. This applies also to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass protective screens, etc.

Attention is directed again to what has been said previously in regard to automatic controls which shut ofi the propylene oxide in event temperature of reaction passes out of the predetermined range or if pressure in the autoclave passes out of predetermined range.

With this particular arrangement practically all oxypropylations become uniform in that the reaction temperature was held within a few degress of any selected point, for instance, if C. was selected as the operating temperature the maximum point would be at the most C. or 112 C., and the lower point would be 95 or possibly 98 C. Similarly, the pressure was held at approximately 30 pounds within a 5-pound variation one way or the other, but might drop to practically zero, especially where no solvent such as xylene is employed. The speed of reaction was comparatively slow under such conditions as compared with oxyalkylations at 200 C. Numerous reactions were conducted in which the time varied from one day (24 hours) up to three days (72 hours), for completion of the final member of a series. In some instances the reaction may take place in considerably less time, i. e., 24 hours or less, as far as a partialoxypropylation is concerned, Theminimumtime recorded was about a 6-hour periodinaasingle step Reactionsindicateda'sbeing complete :il1'17? on 8ih'ourstmay have been complete in'azlesser periodtoftime in light of. the automatic:equipmentemployedi In the addition of propylene so all the propylene oxide-1f fedzcontinuously would be added at a rate: so: that the predetermined amount wouldreact: within the first 5 hours of the 8-hour periodortwo-thirdsxof any shorter period. This'meant' that if the reaction was interrupted automaticallyfor a period of time for pressure to drop ontemperature to drop the predetermined amount ofoxide would still be added in most instanceswellwithin the predetermined time period. Sometimes where theaddition was a comparatively small amount map 8'- speeding up of the reaction; by simply'repeating the example and using-34:, 5- or 6 hours instead of 8 hours.

When operating at a comparatively high temperature, for instance; between 150 to 200 (3., an unreacted alkyleneoxide such as propylene the propylene oxide goes in as a and if it remains unreacted there is, inherent danger and" appropriate steps must be taken" to safeguardagainst this possibility; if need be asample must be withdrawn and examined :for unreacted propylene oxide. One obvious procedure, of course, is to oxypropylate at a modestly highertemperature, for instance, at 140 to 150 0.. Unreacted oxide affects determination of the acetylor hydroxyl value of the hydroxylated'compoun'dobtained.

happen that liquid. Disc, of course, an

that the molecule, being-larger; the opportunity for random reactionis-decreased. Inversely, the lower the molecular weight the faster the reaction takes place. For this reason, ometimes at or ten days-time may lapse; to the higher molecular Weightderivatives from monohydrie orfdihydric materials.

In a number of operations the counterbalance scale or dial scale holding the propylene oxide bomb was so set that amount of propylene oxide had passed into the obtainsome of when' the predetermined 10 The pressuring" of the propylene oxide:- into? the reaction vessel was also automaticinsofar that the feed stream was set for a slow continuous run which entire equipment. As far as Iamaware at least two'firms, and possibly three, specialize in autoclave equipment such as I have employedin the laborator, and are prepared to furnish equipment of this same kind. Similarly pilot plant oxide, glycide, propylene oxide, etc., be conducted except in equipment specially designed for the purpose.

It is to be noted in the present instance one may: or may not have basic nitrogen atoms present. For example, if a phenyl radical is-attached to each nitrogen atomthe-initial triamine is substantially nonbasic. However, if one employs dipropylenetriamine there are present 3' basie nitrogen atoms and thus the addition of an alkaline catalyst can be eliminated in theearly stages of oxypropylation or oxyethylation.

Example 1a The particular autoclave employed was one with a capacity of approximately 15 gallons or'on the average of about pounds of reaction mass. The speed of the stirrer could be varied from to 350 R. P. M. The initial charg was '7 pounds of dipropylene triamine. Even though this reagent itself is alkaline .75 were added. The reaction pot was flushed'out with nitrogen, the autoclave sealed, and the automatic devices set for injecting pylene oxide in approximately 9 action could take place, and probably did'take place, at an appreciably lower: pressure. This comparatively low pressure as the result of the fact that the reactant per so was basic and also because considerable catalyst portant, the selected temperature was within the range of 250 to 260 F. (moderately higher than the boiling p'ointof water); The initial introduction of propylene oxide wasn'ot" started until the heating devices hadraised the temperature to about 240 F., somewhat higher than the boiling point of water. At the completion of the reaction a sample was taken; and oxypropylation continued as in Example 2a, immediately following.

Example 2a 36.26 pounds of reaction mass identified as Example 1a,,

pylene oxide. No additional catalyst was added. The oxypropylation was conducted in substantially. thesame manner in regard to temperature and pressure as in Example. 10;, preceding. The time period was shorter; to wit, about-2 hours. Theoxide was added fairly rapidly, about 15 to 20 ounds per hour. At the end of the reaction period part ofthe'sample was withdrawn and subjected to further oxypropylation as described in Example 3a, following.

Example 3a 45.75 pounds of the reaction mass identified as Example 20., preceding, equivalent to 2.79 pounds of the polyamine, 42 .66 pounds of and .30 pound of caustic soda, were subjected to further oxypropylation in the same manner as described in the two precedin examples. No additional catalyst was introduced. The amount of propylene oxide added was 27.25 pounds. The conditions of reaction as far as temperature and pressure were concerned were the same as in the two preceding examples. The time period was 3 hours. The oxide was added at the rate of a little over 10 pounds per hour. When the reaction was complete part of the sample was withdrawn and the remainder subjected to further oxypropylation as described in Example 4a, im-

mediately following.

Example 400 43.75 pounds of the reaction mass identified as Example 3a, preceding, and equivalent to 1.67 pounds of the polyamine, 41.90 pounds of propylene oxide and .18 pound of caustic soda were subjected to further oxypropylation. No additional catalyst was added. Conditions as far as temperature and pressure were concerned were the same as in the two preceding examples. The time period was 4 hours. The amount-of oxide added was 26.75 pounds. The oxide was added at the rate of about 10 pounds per hour. At the completion of the reaction part of the same was withdrawn and the remainder subjected to further oxypropylation as described in Example a, immediately following.

Example 511 49 pounds of reaction mass identified as Example 4a, preceding, and equivalent to 1.16 pounds of the polyamine, 4'7 .72 pounds of propylene oxide, and .12 pound of caustic soda, were subjected to further oxypropylation without the addition of any more catalyst. Conditions as far as temperature and pressure were concerned were the same as in preceding examples. The amount of oxide added was 15.75 pounds. This oxide was added in 4 hours at the rate of hour.

What has been said herein is presented in tabuar form in Table 1 immediately following with aome added information as to molecular weight but insoluble in kerosene; Example 2a was emulsifiable in water, soluble in xylene but insoluble in kerosene; Examples 311 and 4a were both insoluble in water, soluble in xylene and insoluble in kerosene; and Example 5a was insoluble propylene oxide,

about 5 to 6 pounds per water, but soluble in both xylene and kerosene.

Referring to the first series of compounds, Examples la through 5a, in a similar series I have prepared compounds in which the theoretical molecular weights ran as high as 9,000 to 12,000 and higher with hydroxyl molecular weights running from in excess of 3,000 to 4,000 or higher. Under these circumstances the products prior to esterification were water-insoluble, xylene-soluble and kerosene-soluble.

The final product, i. e., at the end of the oxypropylation step, was apt to be either a faint straw color, or sometimes it would have a more definite dark amber to black-reddish tinge. In the later stages the product was invariably waterinsoluble and kerosene-soluble. This is characteristic of all the products obtained from the triamino products herein described. Needless to say if more ethylene oxide radicals were introduced into the initial raw material the initial product is more water-soluble and one must go to higher molecular weights to produce water-insolubility and kerosene-solubility, for instance, molecular weights such as 8,000 to 12,000 or more on a theoretical basis, and 3,000 to 4,000 or 5,000 on a hydroxyl molecular weight basis. If, however, the initial triamino compound is treated with one or more or perhaps several moles of butylene oxide then the reverse effect is obtained and it takes 30 less propylene oxide to produce water-insolubility and kerosene-solubility. These products were, of course, slightly alkaline due in part to the residual caustic soda employed. This would also be the case if sodium methylate were used as a catalyst.

Speaking of insolubility in water or solubility in kerosene such solubility test can be made simply by shaking small amounts of the materials in a test tube with water, for instance, using 1% to 5% approximately based on the amount of water present.

Needless to say, there is no complete conversion of propylene oxide into the desired hydroxylated compounds. This is indicated by the fact that the theoretical molecular weight based on a statistical average is greater than the molecular weight calculated by usual methods on basis of acetyl or hydroxyl value. Actually, there is no completely satisfactory method for determining molecular weights of these types of compounds with a high degree of accuracy when the molecular weights exceed 2,000. In some instances the acetyl value or hydroxyl value serves as satisfactorily as an index to the molecular weight as any other procedure, subject to the above limitations, and espeand as to solubility of the reaction product in cially in the higher molecular weight range. If water, xylene and kerosene. any difficulty is encountered in the manufacture TABLE 1 Composition Before Composition at End M W Max. Ex. b .11 Max. Pres Time, No. Amine Oxide Oata- Theo. Amine Oxide Catag fi Temp.,F. lbs. sq. hrs. Amt, Amt, Mol. Amt, Amt, lyst, e in.

lbs. lbs. lbs. Wt. lbs. lbs. lbs. 1a.- 7.0 .75 1,200 7.0 57.0 .75 1,002 250-200 05-07 0 2a.- 0.02 01.02 .42 2,100 2.02 50.01 .42 1,140 250-200 35-07 2 3a.. 2.70 42.00 .00 0,410 2.70 00.01 .00 1,002 250-200 05-07 0 45.. 1.07 41.00 .18 5,510 1.07 68.05 .10 2.175 250-200 05-07 4 5a.- 1.10 47. 72 .12 7,200 1.10 00.47 .12 2,742 250-200 05-07 4 Example 1a was soluble in water and xylene, 7 of the esters as described in Part 2 the stoichiometrical amount of acid or acid compound should be taken which corresponds to the indicated acetyl or hydroxyl value. This matter has been discussed in the literature and is a matter of 75 common knowledge and requires no further ela- 1 3 boration. In fact, it is illustrated-by somexoftthe examples appearing in; the patent previously mentioned.

PART 2 the oxypropylated derivatives.- described' in'Part 1, immediately preceding, andpolycarboxyacids,

particularly tricarboxy acids like citric and dicarboxyacids'such-as adipic acid, phthalic acid, or anhydride, succinic acid, diglycollic acid, sebacic acid, azelaic acid; aconitric acid, maleic acid or anhydride, .citraconic acidor anhydride; maleic or anhydride'adducts as obtained" by the Diels-Alder reaction from products suchasimaleic anhydride, and cyclopentadiene. Such acids should be heatistable so they are not decomposed compounds obtained as described in Part1, preceding, contain nitrogen atoms which may or not be basic. Thus, itiis probable particularly Where there is a basic nitrogenatom'present that salts may be formedbut in any-event under conditions described the salt is converted into an ester. This is comparable to similar reactions involving the esterificationv of triethanolamine. Possibly the addition of an acid suchas hydrochloric acid if employedfor elimination of. the basic catalyst also combines-Withv the; basic nitrogen present to form a salt. In any event, hot e er, such proceduredoes. not affectconventional esterification procedure as described herein.

Needless to say, various compounds may be used such as the low molal ester, the anhydride, the acylchloride, etc. However, for purpose'of economy it is customary to use either the acid or the anhydride. A conventional procedure is employed. On a laboratory scale one can employ a resin pot of the kind described in U. S. Patent No. 2,499,379, dated March '7, 1950, to De Groote and Kelser, and particularly with one rnore opening to permit the use of a porous spreader if hydrochloric acid. gas is to be used as a catalyst. Such device or absorption spreader consists of minute Alundum thimbleswhich are connected to a glass tube. One can add a sulfonic acidsuch as paratoluene sulfonic acid as a catalyst. There: is some objection to this because in someinstances there is some evidence that this acid catalyst tends to decompose or rearrange the oxypropylated compounds, and particularly likely to do so if the esterification temperature is too high. In the case of polycarboxy acids such asndiglycollic which is strongly acidic: there is no need to add any catalyst. The useof. hydrochloric acid gas has one advantage over paratoluene sulfonic acid and that is at the end of the reaction it can be removed by flushingout with nitrogen, whereas there is no reasonably convenient means available ofremoving the paratoluenef'suh fonic acid or other sulfonic acid employed. If

. 14 hydrochloric-acid is'.=employed-.onezneedionly pass the-gas' through at an:exceedinglyslow rate so as. to keep the: reactionmass acidic. trace of acid'needbe present. I have employed The products obtained in Part1 preceding may containa basicscatalyst. asszageneral procedure I have added an amount of half concentrated The mixture is shaken thoroughly and. allowed to stand overnight. It is then filtered and refluxed with the xylene present until the water can be separatedinaphase separating trap. As soon as the product is. substantially freefrom water the distillation stops; This preliminary step can be carried out in the flask to be used for esterification. If'there is any further deposition of sodium chloride during the reflux stage needless to say a second filtration may be required. In any event the neutral or slightly acidic solution of the oxypropylated derivatives dea 45% solution- To this solution'thereis added a polycarboxylated reactant as previously de. scribed, such asphthalic anhydride, succinic acid or anhydride, diglycollic acid, etc. Themixture is refluxed" until esterification is complete as indicatediby elimination:ofWatr:or: drop in carboxyl value: Needless to say,.if'one;'producesr a halfester. froinan anhydride such las -phthalic anhydride,an-oi-water:- is eliminated:v Howevenifi it is obtained fromdiglycol-lic: acid; for example, water isielirninatedi All suchnproceduresiare' conventional andih'ave'- been so thoroughly described in the: literature that filrt enconsideration' Will be limited" to a" few examplesand a: comprehensive table.

Other. procedures for: eliminating the basic residuallcatalyst, if; any-,.can.- be employed. For

then. add a small amount of anhydrous sodium sulfate (sufii'cient in quantity to take up any water that is present) and then subject the mass to centrifugal force so as to eliminate the hydrated sodium sulfate and probably the sodium acid radicals; the product is characterized by this mere trace of'water certainly interferes with are used and may retard esterification, particularly Where there is no sulfonic acid or hydrochloric acid present as a catalyst. Therefore I have preferred to use the following procedure: I have employed about 200 grams of the polyhydroxylated compound as described in Part 1, preceding; I have added about 60 grams of benzene, and then refluxed this mixture in the glass resin pot using a phase-separating trap until the benzene carried out all the water present as water of solution or the equivalent. Ordinarily this refluxing temperature is apt to be in the neighborhood of 130 to possibly 150 C. When all this water or moisture has been removed I also withdraw approximately 20 grams or a little less benacne and then add the required amount of the carboxy reactant and also about 150 grams of a high boiling aromatic petroleum solvent. These solvents are sold by various oil refineries and, as far as solvent effect act as if they were almost completely aromatic in character. Typical distillation data in the particular type I have employed and found very satisfactory is the following:

I. B. P., 142 C. ml., 200 C. m1., 209 C. m1., 215 C. m1., 216 C. m1., 220 C. m1., 225 C. m1., 230 C. m1., 234 C. 90 m1., 280 C. m1., 237 C. 95 ml., 307 C.

After this material is added, refluxing is continued and, of course, is at a higher temperature, to wit, about 160 to 170 C. If the carboxy reactant is an anhydride needless to say no water of reaction appears; if the carboxy reactant is an acid, water of reaction should appear and should be eliminated at the above reaction temperature. If it is not eliminated I simply separate out another 10 or 20 cc. of benzene by means of the phase-separating trap and thus raise the temperature to 180 or 190 C., or even to 200 C., if need be. My preference is not to go above 200 C.

m1., 242 C. m1., 244 C. m1., 248 C. m1., 252 C. '70 m1., 252 C. m1., 260 C. m1., 264 C. m1., 270 C.

'16 solvent is extremely satisfacdoes not attempt to remove the solvent subsequently except by vacuum distillation and provided there is no objection to a little residue. Actually, when these materials are used for a purpose such as demulsification the solvent might just as well be allowed to remain. If th solvent is to be removed by distillation, and particularly vacuum distillation, then the high boiling aromatic petroleum solvent might well be replaced by some more expensive solvent, such as Decalin or an alkylated Decalin which has a rather definite or close range boiling point. The removal of the solvent, of course, is purely a conventional procedure and requires no elaboration.

In a number of examples comparable to the series immediately following I have mployed the #7-3 solvent instead of xylene. However, xylene alone is perfectly satisfactory where the initial product shows comparatively little or no water-solubility. For instance, Example 2a. previously referred to was emulsifiable in water but not entirely water-soluble. Thus, in Examples 712 through 300, I have found xylene alone to be perfectly satisfactory because the initial polyhydric material was either entirely water-soluble or at the most water-emulsifiable. However, in Examples lb through 61) I have used a xylene-methanol mixture. In such instances xylene was used to the extent of two-thirds of solvent indicated and when all the water was eliminated approximately 35% methanol was added. In this instance a homogeneous solution was obtained. Here, again, any suitable variant could be employed. I

Another obvious procedure, of course, is merely to distill off a solvent such as xylene or solvent #73 and then dissolve the product in a semipolar solvent, such as methanol, ethanol, propanol, etc. It is purely a matter of convenience first employ a non-polar solvent (water-insoluble) to eliminate the water during distillation and then add a suitable polar solvent (hydrophile) to give a. single-phase system.

The use of such tory provided one TABLE 2 Iiieo.

Cnrboxy Renctant s) 163 l. 032 193 Dlclycollc Acid 75. 0 140 163 1.032 193 Oxallc Acid- 70. 5 140 163 1, 032 193 Maleic Anhyd 55. 0 140 163 1, 032 103 Phthalic Anhyd 83. 0 140 103 l, 032 190 Cltraconic Anhyd. 01. 5 140 163 l, 032 193 Aconitic Acid 97. 5 79. 0 147. 5 1, 140 Diglycollc Acid 69. 5 79. 0 147. 5 1, 140 Acid 00. l 79. 0 147. 5 1, 140 52. l 79. 0 147. 5 1. 140 76. 8 79. 0 147. 5 1, 140 58. 0 79.0 147. 5 1, 140 90. 0 49. 5 103 1, 632 40. l 49. 5 103 1, 632 45. 9 49. 5 103 l, 632 35. 8 49. 5 103 1, 632 55.0 49. 5 103 1. 632 41. 0 49. 5 103 l, 632 64. 8 30. 5 77. 5 2, 37.6 30. 5 77. 5 2, 175 35. 2 30. 5 77. 5 2, 175 28.0 30. 5 77. 5 2, 175 42. 5 30. 5 77. 5 2. 175 33. 4 30. 5 77. 5 2, 175 50. 0 23.2 61. 5 2, 742 29. 6 23.2 61. 5 2, 742 28. 8 23. 2 61. 5 2, 742 21. 8 23. 2 61. 5 2, 742 34.0 23.2 61. 5 2.742 24. 4 23. 2 61. 5 2. 742 38. 8

TABLE 3 The procedure for manufacturing the esters has been illustrated by preceding examples. If for any reason reaction does not take place in a y or acetyl value of the oxypropylated derivative and use a stoichiometrically equivalent amount of acid; (b) if the reaction does not proceed with reasonable time up to 12 or 16 hours if need be; (c) if necessary, use of paratoluene sulfonic acid or some other acid as a catalyst provided that the hydroxylated compound is not baslc; (d) if the such as sodium chloride precipitating out. nated, at least for exploration experimentation,

fication.

Even under the most carefully controlled conditions of oxypropylation involving compara tively low temperature and long time of reaction there are formed certain compounds whose compositions is still obscure. Such side reaction products can contribute a substantial proportion of the final cogeneric reaction mixture. Various as to the nature of 18 actant which can be removed by filtration or, if desired, the esterification procedure can be repeated using an appropriately reduced ratio of carboxylic reactan Even the determination of the hydroxyl value and conventional procedure leaves much to be desired due either to the cogeneric materials previously referred to, or for that matter, the presence of any inorganic salts or propylene oxide. Obviously this oxide should be eliminated.

The solvent employed, if any, can be removed from the finished ester by distillation and particularly vacuum distillation. The final products or liquids are generally pale amber, amber to reddish-black in color, and show moderate viscosity. They can be bleached with bleaching clays, filtering chars, and the like. However, for the purpose of demulsification or-the like color instance. Needless to say, the same situation applies when one has oxyproyplated polyhydric materials having 4 or more hydroxyls, or the obvious equivalent.

Usually no effort is made to differentiate between oxypropylation taking place, for example,

such as HO(RO)1LH or (RO)1LH in which n has one and only one value, for instance, 14, 15 or 16,

the contribution of the various individual members of the mixture. On a statistical basis, of

pounds.

course, a can be appropriately specified. For

ccrned with a monohydric reactant one cannot draw a single formula and say that by following such procedure one can readily obtain 80% or 90% or 100% of such compound. However, in

the case of at least monohydric initial reactants one can readily draw the formulas of a large number of compounds which appear in some of the probable mixtures or can be prepared as components and mixtures which are manufactured conventionally.

Simply by way of illustration reference is made to the copending application of De Groote, Wirtel and Pettingill, Serial No. 109,791, filed August 11, 1949 (now Patent 1951).

However, momentarily referring again to a monohydric initial reactant it is obvious that if one selects any such simple hydrolxylated compound and subjects such compound to oxyalkylation, such as oxyethylations, or it becomes obvious that one is really producing a polymer of the alkylene oxide except for the terminal group. This is particularly true where the amount of oxide added is comparatively large, for instance, 10, 20, 30, 40, or 50 units. If such compound is subjected to oxyethylation so as to introduce units of ethylene oxide, it is well known that one does not obtain a single constituent which, for the sake of convenience, may be indicated as RO(C2H40)30OH. Instead, one obtains a cogeneric mixture of closely related homologues, in which the formula may be shown as the following, RO(C2H40)1LH, wherein n, as far as the statistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25, and perhaps less, to a point where n may represent or more. Such mixture is, as stated, a cogeneric closely related series of touching homologous commade in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental Principles of Condensation Polymerization, by Flory, which appeared in Chemical Reviews, page 137.

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either experimental or mathematical examination, of indicating the exact promembers of touching homolgous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i. e., the ability to describe how to make the product under consideration and how to repeat such production time after time without difficulty, it is necessary to resort to some other method of description, or else consider the value of n, in formulas such as those which have appeared previously and which appear in the claims, as representing both individual constituents in which n has a single definite value, and also with the understanding that n represents the average statistical value based on the assumption of completeness of reaction.

This may be illustrated as follows: Assume that in any particular example the molal ratio of propylene oxide per hydroxyl is 15 to 1. In a generic formula 15 to 1 could be 10., 20 or some other oxypropylation,

Considerable investigation has been volume 39, No. 1,

2,549,434, granted April 17, I

amount and indicated by 11. Referring to this specific case actually one obtains products in which it probably varies from 10 to 20, perhaps even further. The average value, however, is '15, assuming, as previously stated, that the reaction is complete. The product described by the formula is best described also in terms of method of manufacture.

The significant fact in regard to the oxypropylated polyamines herein described is that in the initial stage they are substantially all watersoluble, for instance, up to a molecular weight of 2,500 or thereabouts. Actually, such molecular weight represents a mixture of some higher molecular weight materials and some lower molecular weight materials. The higher ones are probably water-insoluble. The product may tend to emulsify or disperse somewhat because some of the constituents, being a cogeneric mixture, are water-soluble but the bulk are insoluble. Thus one gets emulsifiability or dispersibility as noted. Such products are invariably xylene-soluble regardless of whether the original reactants were or not. Reference is made to what has been said previously in regard to kerosene-solubility. For example, when the theoretical molecular weight gets somewhere past 6,000 or at approximately 7,000 the product is kerosene-soluble and waterinsoluble. These kerosene-soluble oxyalkylation products are most desirable for preparing the esters. I have prepared hydroxylated compounds not only up to the theoretical molecular weight shown previously, i. e., about 8,000 but some which were much higher. I have prepared them, not only from dipropylenetriamine, but also from oxyethylated or oxybutylated derivatives previously referred to. The exact composition is open to question for reasons which are common to all oxyalkylation. It is interesting to note, however, that the molecular weight based on hydroxyl determinations at this point were considerably less, in the neighborhood of a third or a fourth of the value at maximum point. Referring again to previous data it is to be noted, however, that over the range shown of kerosene-solubility the hydroxyl molecular weight has invariably stayed at two-thirds or five-eighths of the theoretical molecular weight.

It becomes obvious when carboxylic esters are prepared from. such high molecular weight materials that the ultimate esterification product again must be a cogeneric mixture. Likewise, it is obvious that the contribution to the total molecular weight made by the polycarboxy acid is small. By the same token one would expect the effectiveness of the demulsifier to be comparable to the unesterified hydroxylatecl material. Remarkably enough, in many instances the product is distinctly better.

PART 4 As pointed out previously the flnal product obtained is a fractional ester having free carboxyl radicals. Such product can be used as an intermediate for conversion into other derivatives which are effective for various purposes, such as the breaking of petroleum emulsions of the kind herein described. For instance, such product can be neutralized with an amine so as to increase its water-solubility such as triethanolamine, tripropanolamine, oxyethylated triethanolamine, etc. Similarly, such product can be neutralized with some amine which tends to reduce the watersolubili y such as cyclohcxylamin benzylamine. de ylamine. t trad oy amine, ct decylamine. etc- Furthermore, the residual carboxyl radicals can be esterified with alcohols, such as low molal a1- cohols, methyl, ethyl, propyl, butyl, etc., and also high molal alcohols, such as octyl, decyl, cyclohexanol, benzyl alcohol, octadecyl alcohol, etc.

water-in-oil emulsions.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent, is:

l. A hydrophile synthetic product which is an ester of (A) a polycarboxy acid with (B) a high molal oxypropylated monomeric acyclic triamino cal having at least 8 uninterrupted carbon atoms and be composed of elements selected from the group consisting of carbon, hydrogen, oxygen and nitrogen; (12) the monomeric triamino compound have a molecular weight of not over 800 and at least a plurality of reactive hydrogen atoms; (0) the oxypropylated monomeric triamino compound have a molecular weight of 2500 to 30,000 on an average statistical basis; (d) the pound be within the range of 7 to 70; (e) the monomeric triamino compound represent not more than 20% by weight of the oxypropylated monomeric triamino compound on a statistical basis; (1) the preceding provisos being based on the assumption of complete reaction between the propylene oxide and the monomeric triamino atoms.

2. A product as in claim 1 in which at least one of the nitrogen atoms of the oxypropylated monomeric triamino compound is basic.

3. A product as in claim 1 in which both nitrogen atoms of the oxypropylated monomeric triamino compound are basic.

4. A product as in claim 3 in which the polycarboxy acid is a dicarboxy acid.

5. A product as in claim 4 in which the mono acid is diglycollic acid.

7. The product of claim 1 wherein the dicarboxy acid is maleic acid.

8. The product of claim 1 wherein the dicarboxy acid is phthalic acid.

9. The product of claim 1 wherein the dicarboxy acid is citraconic acid.

10. The product of claim 1 wherein the dicar boxy acid is succinic acid.

No references cited. 

1. A HYDROPHILE SYNTHETIC PRODUCT WHICH IS AN ESTER OF (A) A POLYCARBOXY ACID WITH (B) A HIGH MOLAL OXYPROPYLATED MONOMERIC ACYCLIC TRIAMINO COMPOUND WITH THE PROVISO THAT (A) THE MONOMERIC TRIAMINO COMPOUND BE FREE FROM ANY RADICAL HAVING AT LEAST 8 UNINTERRUPTED CARBON ATOMS AND BE COMPOSED OF ELEMENTS SELECTED FROM THE GROUP CONSISTING OF CARBON, HYDROGEN, OXYGEN AND NITROGEN; (B) THE MONOMERIC TRIAMINO COMPOUND HAVE A MOLECULAR WEIGHT OF NOT OVER 800 AND AT LEAST A PLURALITY OF REACTIVE HYDROGEN ATOMS; (C) THE OXYPROPYLATED MONOMERIC TRIAMINO COMPOUND HAVE A MOLECULAR WEIGHT OF 2500 TO 30,000 ON AN AVERAGE STATISTICAL BASIS; (D) THE RATIO OF PROPYLENE OXIDE PER INITIAL REACTIVE HYDROGEN ATOM OF THE MONOMERIC TRIAMINO COMPOUND BE WITHIN THE RANGE OF 7 TO 70; (E) THE MONOMERIC TRIAMINO COMPOUND REPRESENT NOT MORE THAN 20% BY WEIGHT OF THE OXYPROPYLATED MONOMERIC TRIAMINO COMPOUND ON A STATISTICAL BASIS; (F) THE PRECEDING PROVISOS BEING BASED ON THE ASSUMPTION OF COMPLETE REACTION BETWEEN THE PROPYLENE OXIDE AND THE MONOMERIC TRIAMINO COMPOUND; (G) THE NITROGEN ATOMS ARE LINKED BY PROPYLENE RADICALS; (H) THE RATIO OF POLYCARBOXY ACID TO OXYPROPYLATED MONOMERIC TRIAMINO COMPOUND BEING ONE MOLE OF THE FORMER FOR EACH REACTIVE HYDROGEN ATOM OF THE LATTER; AND (I) THE POLYCARBOXY ACID BE SELECTED FROM THE GROUP CONSISTING OF ACYCLIC AND ISOCYCLIC DICARBOXY AND TRICARBOXY ACIDS COMPOSED OF CARBON, HYDROGEN AND OXYGEN AND HAVING NOT MORE THAN 8 CARBON ATOMS. 